KR101260597B1 - Metal polishing liquid and method for polishing film to be polished - Google Patents
Metal polishing liquid and method for polishing film to be polished Download PDFInfo
- Publication number
- KR101260597B1 KR101260597B1 KR1020117006918A KR20117006918A KR101260597B1 KR 101260597 B1 KR101260597 B1 KR 101260597B1 KR 1020117006918 A KR1020117006918 A KR 1020117006918A KR 20117006918 A KR20117006918 A KR 20117006918A KR 101260597 B1 KR101260597 B1 KR 101260597B1
- Authority
- KR
- South Korea
- Prior art keywords
- metal
- acid
- polishing
- polishing liquid
- water
- Prior art date
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- 238000005498 polishing Methods 0.000 title claims abstract description 255
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 151
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- 238000000034 method Methods 0.000 title claims abstract description 36
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Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/14—Anti-slip materials; Abrasives
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B24—GRINDING; POLISHING
- B24B—MACHINES, DEVICES, OR PROCESSES FOR GRINDING OR POLISHING; DRESSING OR CONDITIONING OF ABRADING SURFACES; FEEDING OF GRINDING, POLISHING, OR LAPPING AGENTS
- B24B37/00—Lapping machines or devices; Accessories
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09G—POLISHING COMPOSITIONS; SKI WAXES
- C09G1/00—Polishing compositions
- C09G1/02—Polishing compositions containing abrasives or grinding agents
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/14—Anti-slip materials; Abrasives
- C09K3/1454—Abrasive powders, suspensions and pastes for polishing
- C09K3/1463—Aqueous liquid suspensions
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
- H01L21/304—Mechanical treatment, e.g. grinding, polishing, cutting
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
- H01L21/3205—Deposition of non-insulating-, e.g. conductive- or resistive-, layers on insulating layers; After-treatment of these layers
- H01L21/321—After treatment
- H01L21/32115—Planarisation
- H01L21/3212—Planarisation by chemical mechanical polishing [CMP]
-
- C11D2111/22—
Abstract
(a)고체입자에 유래하는 연마 손상의 발생, (b)딧싱, 이로젼 등의 평탄성 악화의 발생, (c)연마 후의 기판 표면에 잔류하는 연마입자를 제거하기 위한 세정 공정의 복잡성, (d)고체 연마입자 자체의 원가나 폐액 처리에 기인하는 비용증가 등의 문제를 해결하고, 또한 높은 Cu 연마속도에서 CMP 가능한 금속용 연마액 및 이를 이용한 피연마막의 연마방법을 제공한다. 금속의 산화제, 산화금속 용해제, 금속 방식제 및 중량평균분자량이 8000 이상의 음이온성 관능기를 가지는 수용성 폴리머를 함유하고, pH가 1 이상 3 이하인 금속용 연마액 및 연마정반의 연마포 상에 상기 금속용 연마액을 공급하면서, 피연마 금속막을 가지는 기판을 연마포에 압압한 상태에서 연마정반과 기판을 상대적으로 작동시켜 연마하는 것을 특징으로 하는 피연마막의 연마 방법.(a) the occurrence of abrasive damage resulting from solid particles, (b) the deterioration of flatness such as dicing and erosion, (c) the complexity of the cleaning process to remove abrasive particles remaining on the substrate surface after polishing, (d The present invention solves the problems such as the cost of solid abrasive particles themselves and the cost increase due to waste liquid treatment, and also provides a polishing solution for metals capable of CMP at a high Cu polishing rate and a polishing method using the same. The metal oxidant, the metal oxide dissolving agent, the metal anticorrosive agent, and the weight average molecular weight containing the water-soluble polymer having an anionic functional group of 8000 or more and having a pH of 1 to 3 or less for the metal and the polishing cloth for the polishing plate for the metal. A polishing method for polishing a polishing film, wherein the polishing table and the substrate are relatively operated while the substrate having the polishing metal film is pressed against the polishing cloth while the polishing liquid is supplied.
Description
본 발명은, 금속용 연마액 및 피연마막의 연마 방법에 관한 것이다. The present invention relates to a polishing method for a polishing liquid for metal and a polished film.
최근, 반도체집적회로(이하, LSI로 기재한다.)의 고집적화, 고성능화에 수반하여 새로운 미세 가공 기술이 개발되고 있다. 화학기계 연마(이하, CMP로 기재한다.)법도 그 하나이며, LSI 제조공정, 특히 다층배선 형성 공정에 있어서의 층간절연막의 평탄화, 금속 플러그 형성, 매입 배선 형성 등에 있어서 빈번히 이용되는 기술이며, 예를 들면, 미국 특허 제4,944,836호 명세서에 개시되어 있다.In recent years, new fine processing techniques have been developed with high integration and high performance of semiconductor integrated circuits (hereinafter referred to as LSI). The chemical mechanical polishing (hereinafter referred to as CMP) method is one such technique, which is frequently used in the planarization of an interlayer insulating film, metal plug formation, embedded wiring formation, etc. in an LSI manufacturing process, particularly a multilayer wiring formation step. See, for example, US Pat. No. 4,944,836.
또한, 최근에는 LSI를 고성능화하기 위해서, 배선재료로서 구리합금의 이용이 시험되고 있다. 그러나, 구리합금은 종래의 알루미늄합금 배선의 형성에서 빈번히 이용된 드라이에칭법에 의한 미세 가공이 곤란하다. 따라서, 예를 들면, 미리 구(構)를 형성하고 있는 절연막 상에 구리합금 박막을 퇴적(堆積)하여 매입하고, 구부(構部: groove portion)이외의 구리합금 박막을 CMP에 의해 제거하여 매입 배선을 형성하는, 이른바 다마신법이 주로 채용되고, 예를 들면, 일본 특허공개공보 평2-278822호에 개시되어 있다. In recent years, the use of a copper alloy as a wiring material has been tested to improve the performance of LSI. However, the copper alloy is difficult to be finely processed by the dry etching method frequently used in the formation of conventional aluminum alloy wiring. Therefore, for example, a copper alloy thin film is deposited and embedded on the insulating film which has previously formed the sphere, and copper alloy thin films other than the groove portion are removed by CMP and embedded. The so-called damascene method for forming wiring is mainly employed, and is disclosed in, for example, Japanese Patent Laid-Open No. 2-278822.
금속의 CMP의 일반적인 방법은, 원형의 연마정반(플래튼-platen) 위에 연마 패드를 붙이고, 연마 패드 표면을 금속용 연마액에 침지하고, 기판의 금속막을 형성한 면을 눌러 붙이고, 그 이면으로부터 소정의 압력(이하, 연마 압력으로 기재한다.)을 가한 상태에서 연마정반을 돌려, 연마액과 금속막의 볼록부와의 기계적 마찰에 의해서 볼록부의 금속막을 제거하는 것이다.The general method of CMP of metal is to apply a polishing pad on a circular polishing platen, to immerse the surface of the polishing pad in a polishing liquid for metal, to press the surface on which the metal film of the substrate is formed, and to press from the back surface thereof. The polishing platen is turned under a predetermined pressure (hereinafter referred to as polishing pressure) to remove the metal film of the convex portion by mechanical friction between the polishing liquid and the convex portion of the metal film.
CMP에 이용되는 금속용 연마액은, 일반적으로는 산화제 및 연마입자로 이루어져 있고, 필요에 따라 산화금속 용해제, 금속 방식제 등이 더 첨가된다. 우선, 산화에 의해서 금속막 표면을 산화하고, 그 산화층을 연마입자에 의해서 제거하는 것이 기본적인 메커니즘으로 생각되고 있다. 오목부의 금속 표면의 산화층은 연마 패드에 거의 접하지 않고, 연마입자에 의한 제거 효과가 미치지 않기 때문에, CMP의 진행과 함께 볼록부의 금속층이 제거되어 기판 표면은 평탄화된다(예를 들면, 저널·오브·일렉트로 케미컬 소사이어티지, 제138 권11호(1991년 발행), 3460~3464페이지 참조).The polishing liquid for metals used for CMP generally consists of an oxidizing agent and abrasive grains, A metal oxide dissolving agent, a metal anticorrosive, etc. are further added as needed. First, oxidizing the surface of a metal film by oxidation and removing the oxide layer by abrasive grains is considered as a basic mechanism. Since the oxide layer of the metal surface of the concave portion is hardly in contact with the polishing pad and does not have a removal effect by the abrasive particles, the metal layer of the convex portion is removed with the progress of CMP, and the substrate surface is flattened (for example, a journal of Electro Chemical Society, Vol. 138, No. 11 (published in 1991), pages 3460-3464).
그렇지만, 종래의 연마입자를 포함하는 금속용 연마액을 이용하여 CMP에 의한 매입 배선 형성을 실시하는 경우에는, (a)고체입자에 유래하는 연마 손상의 발생, (b)매입된 금속배선의 표면 중앙부분이 등방적으로 연마되어 접시와 같이 움푹 팬 현상(이하, 딧싱(dishing)이라 기재한다.), 배선 금속과 함께 층간절연막이 연마되어 움푹 팬 현상(이하, 이로젼(errosion)으로 기재한다.), 등의 평탄성 악화의 발생, (c)연마 후의 기판 표면에 잔류하는 연마입자를 제거하기 위한 세정 공정의 복잡성, (d)고체 연마입자 자체의 원가나 폐액 처리에 기인하는 비용증가, 등의 문제가 발생한다.However, in the case of forming embedded wirings by CMP using a conventional polishing liquid for metal containing abrasive particles, (a) the occurrence of polishing damage resulting from solid particles, and (b) the surface of the embedded metal wirings The central part is isotropically polished to form a recessed pan phenomenon like a dish (hereinafter referred to as “dishing”), and an interlayer insulating film is polished together with a wiring metal to form a recessed pan phenomenon (hereinafter referred to as an erosion). Occurrence of flatness deterioration, etc., (c) complexity of cleaning process for removing abrasive particles remaining on the surface of the substrate after polishing, (d) increased cost due to the cost of the solid abrasive particles themselves or waste liquid treatment, etc. Problem occurs.
평탄성 악화의 해결로서 딧싱, 이로젼, 연마 손상의 발생을 억제하고, 신뢰성이 높은 LSI 배선을 형성하기 위해서, 글리신 등의 아미노아세트산 또는 아미드황산으로 이루어지는 산화금속 용해제, BTA(벤조트리아졸) 등의 보호막 형성제를 함유하는 금속용 연마액을 이용하는 방법 등이 제창되고 있다(예를 들면, 일본 특허공개공보 평8-83780호 참조). 그러나, BTA 등의 보호막 형성 효과에 의해 평탄성 악화를 해결하는 방법은, 딧싱 및 이로젼의 발생을 억제할 수 있지만, 연마속도가 현저하게 저하되어 바람직하지 않은 경우가 있다.In order to solve the deterioration of flatness, in order to suppress occurrence of dicing, erosion and polishing damage and to form a highly reliable LSI wiring, a metal oxide dissolving agent composed of aminoacetic acid or amic sulfuric acid such as glycine, BTA (benzotriazole) and the like The method of using the polishing liquid for metals containing a protective film forming agent, etc. are proposed (for example, refer Unexamined-Japanese-Patent No. 8-83780). However, the method of solving flatness deterioration by the protective film forming effect, such as BTA, can suppress the occurrence of dicing and erosion, but the polishing rate is considerably lowered in some cases, which is undesirable.
한편, CMP 처리에 의해 기판에 부착한 연마입자의 제거는, 폴리비닐알코올제 브러쉬나 초음파에 의한 물리적인 세정으로 주로 행해지고 있다. 그렇지만, 기판에 부착하는 연마입자가 미세화하는 것에 따라, 연마입자에 대해서 물리력을 유효하게 작용시키는 것이 곤란해질 수 있다.On the other hand, the removal of the abrasive grains affixed to the substrate by the CMP process is mainly performed by physical washing with a polyvinyl alcohol brush or ultrasonic waves. However, as the abrasive grains adhered to the substrate become finer, it may be difficult to effectively exert a physical force on the abrasive grains.
이것에 대하여 금속막, 특히 구리 혹은 구리를 주체로 한 금속의 연마액으로서, 실질적으로 연마입자를 포함하지 않은 연마액이, 예를 들면, 일본 특허 제3371775호 명세서에 개시되어 있다. 그에 따르면, 피연마 금속막을 산화하기 위한 산화성물질과, 상기 산화성물질로 산화된 산화물을 수용성화하는 유기산과, 물과, 필요하다면 방식성 물질(보호막 형성제)을 포함하는 연마액을 이용하고, 금속 표면에 기계적인 마찰을 가함으로써 매입 금속배선을 형성할 수 있다. 예를 들면, 과산화수소와 구연산과 벤조트리아졸을 포함하는 실질적으로 연마입자를 포함하지 않는 연마액으로 구리 배선을 형성하는 방법이 일례로서 기재되어 있고, 상술의 (a)~(d)의 문제는 해결되고 있다. 그러나, 이 방법으로는 통상의 연마 조건에 있어서의 연마속도가 80~150nm/분이고, 300g/cm2 이상의 높은 연마 하중을 걸어도 연마속도가 포화하여 200nm/분을 넘지 않는다는 문제가 있고, 이 문제에 대해서, 산화성물질, 인산, 유기산, 보호막 형성제 및 물을 포함하여 실질적으로 연마입자를 포함하지 않은 금속 연마액을 이용하여, 금속 표면에 기계적인 마찰을 가함으로써 매입 금속배선을 형성하는 방법이 제안되어 있다(일본 특허공개공보 제2002-50595호 참조). 이 방법으로는 상술한 (a)~(d)의 문제를 해결하고, 또한 연마속도의 고속화(700nm/분 이상)를 실현할 수 있고, 딧싱이나 이로젼이 약 50nm 이하가 되는 형상으로 가공할 수 있다는 기재가 있다. 실질적으로 연마지립을 포함하지 않는 금속용 연마액 때문에, 이로젼의 발생량은 상당히 적었다.On the other hand, as a polishing liquid of a metal film, especially a metal mainly composed of copper or copper, a polishing liquid substantially free of abrasive particles is disclosed in, for example, Japanese Patent No. 3371775. According to this, a polishing liquid containing an oxidizing material for oxidizing the polished metal film, an organic acid that water-solubles the oxide oxidized with the oxidizing material, water and, if necessary, an anticorrosive material (protective film former), The buried metal wiring can be formed by applying mechanical friction to the metal surface. For example, a method of forming a copper wiring with a polishing liquid substantially free of abrasive particles containing hydrogen peroxide, citric acid and benzotriazole is described as an example, and the problems of (a) to (d) described above are It is being solved. However, this method has a problem that the polishing rate under ordinary polishing conditions is 80 to 150 nm / minute, and that even if a high polishing load of 300 g / cm 2 or more is applied, the polishing rate is saturated and does not exceed 200 nm / minute. A method of forming embedded metal wiring by applying mechanical friction to a metal surface using a metal polishing liquid substantially free of abrasive particles, including an oxidizing substance, phosphoric acid, organic acid, a protective film former, and water, is proposed. (See Japanese Patent Laid-Open No. 2002-50595). This method solves the problems of (a) to (d) described above, and can speed up the polishing speed (700 nm / min or more), and can be processed into a shape in which dicing or erosion becomes about 50 nm or less. There is a description. Due to the polishing liquid for metals substantially free of abrasive grains, the amount of erosion generated was quite small.
한편으로, 배선폭이나 배선 밀도에 관한 기재는 없고, 발명자의 실험에 의하면 이 연마액으로 연마한 SEMATECH854 패턴 마스크 웨이퍼의 Cu 배선폭/배선 스페이스=100㎛/100㎛부에 있어서의 Cu 배선부의 딧싱은 100nm 이상이며, 테크놀러지 노드 130nm 이후(hp130)의 레벨의 매입 Cu 배선을 형성하기 위한 금속용 연마액으로서는 이용할 수 없는 것이었다. 여기서, 테크놀러지 노드는 반도체의 기술 세대를 나타내고, DRAM의 워드라인(word line)·비트라인(bit line)의 최소 배선 피치의 반(하프피치)으로 표현되는(예를 들면, 미국 SEMATECH(Semiconductor Manufacturing Technology Institute) 것으로부터 발표되어 있는, ITRS이다(International Technology Roadmap for Semiconductors)의 2003년도판 참조).On the other hand, there is no description of wiring width and wiring density, and according to the inventor's experiment, the wiring of the Cu wiring part in Cu wiring width / wiring space = 100micrometer / 100micrometer part of the SEMATECH854 pattern mask wafer polished with this polishing liquid Is 100 nm or more and was not available as a polishing liquid for metals for forming embedded Cu wiring at the level of technology node 130 nm or later (hp130). Here, a technology node represents a technology generation of semiconductors and is expressed as half (half pitch) of the minimum wiring pitch of a word line and a bit line of a DRAM (for example, US SEMATECH (Semiconductor Manufacturing) Technology Institute (ITRS), published in 2003 by the International Technology Roadmap for Semiconductors.
상술한 바와 같이, 연마지립을 전혀 포함하지 않는, 혹은 극미량의 연마지립을 첨가한 금속용 연마액에 의해서 연마 손상, 이로젼, 연마 후의 연마지립 제거의 필요성, 고체 지립 그 자체의 원가나 폐액 처리에 기인하는 비용증가 등의 문제, 또는 쓰루풋(throughput) 향상을 목적으로 한 연마속도의 문제는 해결되지만, 배선의 신뢰성이나 성능에 크게 기여하는 딧싱의 저감이 곤란했다. 주로 폭이 넓은 배선부에 있어서의 딧싱이 크고, 테크놀러지 노드 130nm 이후의 레벨의 매입 Cu 배선을 형성하기 위한 금속용 연마액으로서는 이용할 수 없는 문제가 있었다.As described above, polishing damage, erosion, necessity of removing the abrasive grains after polishing, and the cost of the solid abrasive itself or waste liquid treatment by the polishing liquid for metals containing no abrasive grains or adding a very small amount of abrasive grains. Problems such as an increase in cost or a problem of polishing speed for the purpose of improving throughput have been solved, but it has been difficult to reduce the dicing, which greatly contributes to the reliability and performance of the wiring. There was a problem that the dicing in the wide wiring part was large, and it could not be used as a polishing liquid for metal for forming embedded Cu wiring at the level after the technology node 130 nm.
본 발명은, (a)고체입자에 유래하는 연마 손상의 발생, (b)딧싱, 이로젼 등의 평탄성 악화의 발생, (c)연마 후의 기판 표면에 잔류하는 연마입자를 제거하기 위한 세정 공정의 복잡성, (d)고체 연마입자 그 자체의 원가나 폐액 처리에 기인하는 비용증가 등의 문제를 해결하고, 또한 높은 Cu 연마속도로 CMP 가능한 금속용 연마액, 즉 테크놀러지 노드 130nm 이후의 레벨의 매입 Cu 배선이 형성가능한 금속용 연마액 및 이것을 이용한 피연마막의 연마 방법을 제공하는 것이다.The present invention provides a cleaning process for (a) occurrence of abrasive damage resulting from solid particles, (b) deterioration of flatness such as dicing and erosion, and (c) removal of abrasive particles remaining on the substrate surface after polishing. Complexity, (d) the cost of solid abrasive particles themselves or the increase in cost due to waste treatment, and also for CMPs capable of CMP at high Cu polishing rates, ie, embedded Cu at 130nm and beyond technology nodes The polishing liquid for metal which can form wiring, and the polishing method of the to-be-polished film using this are provided.
본 발명은, (1)금속의 산화제, 산화금속 용해제, 금속 방식제 및 중량평균분자량이 8,000 이상의 음이온성 관능기를 가지는 수용성 폴리머를 함유하고, pH가 1 이상 3 이하인 것을 특징으로 하는 금속용 연마액에 관한 것이다.The present invention comprises (1) a metal oxidizing agent, a metal oxide dissolving agent, a metal anticorrosive agent, and a weight average molecular weight containing a water-soluble polymer having an anionic functional group of 8,000 or more, and having a pH of 1 or more and 3 or less. It is about.
또한, 본 발명은, (2)상기 금속의 산화제가, 과산화수소, 과황산암모늄, 질산, 과요오드산칼륨, 차아염소산 및 오존수로부터 선택되는 1종 이상의 산화제인 것을 특징으로 하는 상기 (1)에 기재된 금속용 연마액에 관한 것이다.(2) The present invention is characterized in that (2) the oxidizing agent of the metal is at least one oxidizing agent selected from hydrogen peroxide, ammonium persulfate, nitric acid, potassium periodate, hypochlorous acid and ozone water. A polishing liquid for metals.
또한, 본 발명은, (3)상기 산화금속 용해제가, 25℃에 있어서의 제 1단의 산해리정수가 3.7 미만인 무기산, 유기산, 혹은 그 염으로부터 선택되는 1종 이상의 산화금속 용해제인 것을 특징으로 하는 상기 (1) 또는 (2)에 기재된 금속용 연마액에 관한 것이다.(3) The present invention is characterized in that (3) the metal oxide solubilizer is at least one metal oxide solubilizer selected from an inorganic acid, an organic acid, or a salt thereof having an acid dissociation constant of less than 3.7 in the first stage at 25 ° C. It relates to the polishing liquid for metals as described in said (1) or (2).
또한, 본 발명은, (4)상기 산화금속 용해제가, 말론산, 구연산, 사과산, 글리콜산, 글루타민산, 글리콘산, 옥살산, 주석산, 피콜린산, 니코틴산, 만델산, 아세트산, 황산, 질산, 인산, 염산, 개미산, 젖산, 프탈산, 푸말산, 말레인산, 아미노아세트산, 아미드황산 및 그 염으로부터 선택되는 1종 이상의 산화금속 용해제인 것을 특징으로 하는 상기 (1)~(3) 중 어느 한 항에 기재된 금속용 연마액에 관한 것이다.In addition, the present invention, (4) the metal oxide solubilizer is malonic acid, citric acid, malic acid, glycolic acid, glutamic acid, glyconic acid, oxalic acid, tartaric acid, picolinic acid, nicotinic acid, mandelic acid, acetic acid, sulfuric acid, nitric acid, The at least one metal oxide solubilizer selected from phosphoric acid, hydrochloric acid, formic acid, lactic acid, phthalic acid, fumaric acid, maleic acid, aminoacetic acid, amid sulfuric acid and salts thereof, according to any one of the above (1) to (3). The polishing liquid for metals described is related.
또한, 본 발명은, (5)상기 금속 방식제가, 함질소 환상화합물 및 이온성 계면활성제로부터 선택되는 1종 이상의 금속 방식제인 것을 특징으로 하는 상기 (1)~(4) 중 어느 한 항에 기재된 금속용 연마액에 관한 것이다.Moreover, this invention is (5) The said metal anticorrosive agent is 1 or more types of metal anticorrosive agents chosen from a nitrogen-containing cyclic compound and an ionic surfactant, The said any one of said (1)-(4) characterized by the above-mentioned. A polishing liquid for metals.
또한, 본 발명은, (6)상기 음이온성 관능기를 가지는 수용성 폴리머가, 술폰산기, 카르본산기, 인산기, 또는 그 염의 적어도 1종의 음이온성 관능기를 가지는 수용성 폴리머인 것을 특징으로 하는 상기 (1)~(5) 중 어느 한 항에 기재된 금속용 연마액에 관한 것이다.(6) The present invention is characterized in that (6) the water-soluble polymer having an anionic functional group is a water-soluble polymer having at least one anionic functional group of a sulfonic acid group, a carboxylic acid group, a phosphoric acid group or a salt thereof. It relates to the polishing liquid for metals in any one of)-(5).
또한, 본 발명은, (7)금속용 연마액 중량에 대하여, 1중량% 미만의 연마입자를 첨가해서 이루어지는 상기 (1)~(6) 중 어느 한 항에 기재된 금속용 연마액에 관한 것이다.Moreover, this invention relates to the polishing liquid for metals in any one of said (1)-(6) formed by adding less than 1 weight% of abrasive grains with respect to the weight of the polishing liquid for metals (7).
또한, 본 발명은, (8)상기 연마입자가, 실리카, 알루미나, 세리아, 티타니아, 지르코니아, 게르마니아로부터 선택되는 1종 이상의 연마입자인 것을 특징으로 하는 상기 (1)~(7) 중 어느 한 항에 기재된 금속용 연마액에 관한 것이다.In addition, the present invention is (8) any one of the above (1) to (7), wherein the abrasive particles are at least one abrasive grain selected from silica, alumina, ceria, titania, zirconia, and germania. It relates to the polishing liquid for metals described in.
또한, 본 발명은, (9)금속용 연마액의 연마 대상인 피연마 금속이, 구리, 구리합금 및 구리화합물로부터 선택되는 적어도 1종 이상의 금속인 것을 특징으로 하는 상기 (1)~(8) 중 어느 한 항에 기재된 금속용 연마액에 관한 것이다.
(9) In the above (1) to (8), the present invention is characterized in that the to-be-polished metal to be polished of the polishing liquid for metal is at least one or more metals selected from copper, copper alloys and copper compounds. It relates to the polishing liquid for metals in any one of Claims.
*또한, 본 발명은, (10)연마정반의 연마포 상에 상기 (1)~(9) 중 어느 한 항에 기재된 금속용 연마액을 공급하면서, 피연마막을 가지는 기판을 연마포에 압압한 상태로 연마정반과 기판을 상대적으로 작동시켜 연마하는 것을 특징으로 하는 피연마막의 연마 방법으로 한다.Moreover, this invention presses the board | substrate which has a to-be-polished film to a polishing cloth, supplying the polishing liquid for metals as described in any one of said (1)-(9) on the polishing cloth of (10) polishing polishing boards. It is a polishing method of the to-be-polished film characterized by carrying out grinding | polishing with a grinding | polishing base plate and a board | substrate relatively in a state.
본 발명의 금속용 연마액 및 피연마막의 연마 방법에 의하면, 상기 (a)~(d)의 문제를 해결할 수 있고, 또한 높은 연마속도로 낮은 딧싱, 즉 테크놀러지 노드 130nm 이후에 필요하게 되는 레벨의 매입 Cu 배선을 형성할 수 있다.According to the polishing method of the metal polishing liquid and the polished film of the present invention, the problems of (a) to (d) can be solved, and at a high polishing rate, the level required after low dicing, that is, after the technology node 130 nm Embedded Cu wiring can be formed.
이하에, 본 발명의 금속용 연마액에 대해 상세하게 설명한다.EMBODIMENT OF THE INVENTION Below, the polishing liquid for metals of this invention is demonstrated in detail.
종래, 실질적으로 연마지립을 포함하지 않는 금속용 연마액은, 연마속도를 감소시키지 않기 위해서 금속 방식제의 첨가량을 최저한으로 억제하는 것이 요구되고 있었다. 그렇지만, 금속 방식제의 첨가량을 줄이면 연마포와의 접촉면뿐만 아니라, 오목부에 있어서도 등방적인 에칭이 진행되어 딧싱의 발생을 충분히 억제할 수 없었다. 이것에 대해, 여러 가지의 금속용 연마액이 검토되어, 에칭의 억제와 연마속도의 향상을 달성하고 있지만, 테크놀러지 노드 130nm 이후에 필요하게 되는 레벨의 딧싱량의 매입 Cu 배선의 형성은 곤란했다.Conventionally, the polishing liquid for metal which does not contain abrasive grain substantially has been required to suppress the addition amount of a metal anticorrosive agent to the minimum, in order not to reduce a polishing speed. However, when the addition amount of the metal anticorrosive agent was reduced, isotropic etching proceeded not only in the contact surface with the polishing cloth but also in the recessed portion, and it was not possible to sufficiently suppress the occurrence of the dicing. On the other hand, various kinds of polishing liquids for metals have been examined, and the suppression of etching and the improvement of the polishing rate have been achieved. However, it was difficult to form the embedded Cu wiring at the level of the dicing required for the technology node 130 nm and later.
이것에 대해서 본 발명자 등은, 충분히 낮은 pH의 영역에 있어서, 금속 방식제와 중량평균분자량이 8,000 이상의 음이온성 관능기를 가지는 수용성 폴리머를 병용하는 것에 의해, CMP에 적용할 수 있는 충분히 높은 연마속도의 달성과, 테크놀러지 노드 130nm 이후에 필요하게 되는 레벨의 딧싱량의 매입 Cu 배선의 형성이 가능한 것을 발견했다.On the other hand, the present inventors have used a metal anticorrosive agent and a water-soluble polymer having an anionic functional group with a weight average molecular weight of 8,000 or more in a region of sufficiently low pH, thereby achieving a sufficiently high polishing rate applicable to CMP. It was found that it is possible to form a Cu wiring with an amount of dicing of a level required after the technology node 130 nm.
본 발명의 금속용 연마액은, 금속의 산화제, 산화금속 용해제, 금속 방식제 및 중량평균분자량이 8,000 이상의 음이온성 관능기를 가지는 수용성 폴리머를 함유하고, pH가 1 이상 3 이하인 것을 특징으로 한다.The polishing liquid for metals of this invention contains a metal oxidizing agent, a metal oxide dissolving agent, a metal anticorrosive agent, and the water-soluble polymer which has a weight average molecular weight of 8,000 or more anionic functional groups, and has a pH of 1 or more and 3 or less.
본 발명의 금속용 연마액의 pH는 1 이상 3 이하이며, 바람직하게는 1.5 이상 2.8 이하, 더 바람직하게는 1.8 이상 2.5 이하이다. pH가 3을 초과하면 딧싱이 증가하고, 또한, pH가 1 미만이면 배선 금속의 부식이나 에칭에 기인하는 것으로 생각되는 딧싱이 증가해 버린다. pH는, 예를 들면, 금속용 연마액에 첨가하는 산화금속 용해제의 양으로 조정할 수 있다. 또한, 암모니아, 수산화 칼륨 등의 염기를 산화금속 용해제와 병용함으로써 조정하는 것도 가능하다.PH of the polishing liquid for metals of this invention is 1 or more and 3 or less, Preferably it is 1.5 or more and 2.8 or less, More preferably, it is 1.8 or more and 2.5 or less. When the pH exceeds 3, the dicing increases, and when the pH is less than 1, the dicing considered to be due to corrosion or etching of the wiring metal increases. pH can be adjusted with the quantity of the metal oxide solubilizer added to a metal polishing liquid, for example. Moreover, it is also possible to adjust by using bases, such as ammonia and potassium hydroxide, together with a metal oxide solubilizer.
본 발명에 있어서의 pH는, pH미터(예를 들면, 요코가와전기주식회사 제조, Model pH81)로 측정할 수 있다. 측정방법은, 표준 완충액(프탈산염 pH 완충액 pH: 4.21(25℃), 중성인산염 pH 완충액 pH6.86(25℃))을 이용하여 2점 구성한 후, 전극을 연마액에 넣고, 2분 이상 경과하여 안정한 후의 값을 연마액의 pH로 했다.PH in this invention can be measured with a pH meter (for example, Yokogawa Electric Co., Model pH81). After measuring two points using a standard buffer solution (phthalate pH buffer pH: 4.21 (25 degreeC), neutral phosphate pH buffer pH6.86 (25 degreeC)), an electrode was put into polishing liquid and 2 minutes or more passed. And the value after stabilization was made into the pH of polishing liquid.
본 발명에 있어서의 금속의 산화제로서는, 과산화수소(H2O2), 질산, 과요오드산 칼륨, 과황산암모늄, 차아염소산, 오존수 등을 들 수 있고, 이들 중에서도 과산화수소가 바람직하다. 이들 산화제는 1종류 단독으로, 혹은 2종 이상을 조합시켜서 사용할 수 있다. 기판이 집적회로용 소자를 포함하는 실리콘기판인 경우, 알칼리금속, 알칼리토류금속, 할로겐화물 등에 의한 오염은 바람직하지 않기 때문에, 불휘발성분을 포함하지 않는 산화제가 바람직하고, 그 중에서도 안정성의 면에서 과산화수소가 바람직하다.Examples of the metal oxidizing agent in the present invention include hydrogen peroxide (H 2 O 2 ), nitric acid, potassium periodate, ammonium persulfate, hypochlorous acid, ozone water, and the like. Among them, hydrogen peroxide is preferred. These oxidizing agents can be used individually by 1 type or in combination of 2 or more type. In the case where the substrate is a silicon substrate including an integrated circuit device, contamination by alkali metals, alkaline earth metals, halides, etc. is undesirable, and therefore, an oxidant containing no nonvolatiles is preferable, and among them, in terms of stability, Hydrogen peroxide is preferred.
본 발명에 있어서의 산화제의 배합량은 적의 선택되지만, 연마액 전체 중량에 대하여, 3~20중량%인 것이 바람직하고, 5~15중량%인 것이 보다 바람직하다. 산화제의 배합량이 3중량% 미만인 경우는, 충분한 연마속도가 얻어지지 않는 경향이 있고, 20중량%를 초과하는 경우에도 마찬가지로 충분한 연마속도가 얻어지지 않는 경향이 있다.Although the compounding quantity of the oxidizing agent in this invention is suitably selected, it is preferable that it is 3-20 weight% with respect to the polishing liquid total weight, and it is more preferable that it is 5-15 weight%. When the blending amount of the oxidizing agent is less than 3% by weight, a sufficient polishing rate tends not to be obtained, and even when it exceeds 20% by weight, a sufficient polishing rate tends not to be obtained.
본 발명에 있어서의 산화금속 용해제는, 25℃에 있어서의 제 1단의 산해리지수(pK1)가 바람직하게는 3.7 미만, 더 바람직하게는 2.0~3.7인 무기산 또는 유기산, 혹은 그 염으로부터 선택되는 1종 이상의 수용성의 산화금속 용해제이다. 이러한 산화금속 용해제는, 예를 들면, 말론산, 구연산, 사과산, 글리콜산, 글루타민산, 글리콘산, 옥살산, 주석산, 피콜린산, 니코틴산, 만델산, 아세트산, 황산, 질산, 인산, 염산, 개미산, 젖산, 프탈산, 푸말산, 말레인산, 아미노아세트산, 아미드황산, 혹은 그 암모늄염이나 칼륨염 등을 들 수 있다. 이들 산화금속 용해제는 보호막 형성제와의 밸런스를 얻기 쉬운 점에서 바람직하다. 이들 중에서도, 실용적인 CMP 속도를 유지하면서, 에칭속도를 효과적으로 억제할 수 있는 점에서, 사과산, 주석산, 구연산, 인산, 황산이 바람직하고, 사과산, 인산, 황산이 보다 바람직하다. 이들 산화금속 용해제는 1종류 단독으로, 혹은 2종 이상을 조합시켜서 사용할 수 있다.The metal oxide solubilizing agent in the present invention is 1 selected from inorganic or organic acids or salts thereof, wherein the acid dissociation index (pK1) of the first stage at 25 ° C is preferably less than 3.7, more preferably 2.0 to 3.7. It is a water-soluble metal oxide dissolving agent of more than a species. Such metal oxide solubilizers are, for example, malonic acid, citric acid, malic acid, glycolic acid, glutamic acid, glyconic acid, oxalic acid, tartaric acid, picolinic acid, nicotinic acid, mandelic acid, acetic acid, sulfuric acid, nitric acid, phosphoric acid, hydrochloric acid, formic acid And lactic acid, phthalic acid, fumaric acid, maleic acid, amino acetic acid, amide sulfuric acid, and ammonium salts and potassium salts thereof. These metal oxide solubilizers are preferable at the point which is easy to obtain the balance with a protective film formation agent. Among these, malic acid, tartaric acid, citric acid, phosphoric acid and sulfuric acid are preferable, and malic acid, phosphoric acid and sulfuric acid are more preferable at the point which can effectively suppress an etching speed, maintaining a practical CMP speed. These metal oxide solubilizers can be used individually by 1 type or in combination of 2 or more type.
본 발명에 있어서, 높은 연마속도와 낮은 딧싱을 달성하기 위해서는 수용성 폴리머의 음이온성 관능기의 해리를 억제할 필요가 있다. 음이온성 관능기의 해리를 억제하려면 제 1단의 산해리지수가 낮은 산을 첨가하는 것이 효과적이며, 구체적으로는 제 1단의 산해리지수가 3.7 미만인 수용성의 산화금속 용해제가 수용성 폴리머의 음이온성 관능기의 해리의 억제에 유용한 것을 확인했다. 또한, 본 발명에 있어서의 산해리지수는, 산해리정수의 역수의 대수값으로, 예를 들면 일본 「화학편람기초편」개정 4판(평성 5년 9월 30일 발행), 마루젠주식회사, II-317~321페이지에 상세한 기재가 있다.In the present invention, it is necessary to suppress dissociation of the anionic functional group of the water-soluble polymer in order to achieve high polishing rate and low dicing. In order to suppress dissociation of the anionic functional group, it is effective to add an acid having a low acid dissociation number in the first stage. Specifically, a water-soluble metal oxide dissolving agent having an acid dissociation number of the first stage is less than 3.7, and dissociation of the anionic functional group in the water-soluble polymer. It was found to be useful for the suppression of. The acid dissociation constant in the present invention is an algebraic value of the reciprocal of the acid dissociation constant, for example, the 4th edition of `` Chemical Handbook Basic Edition '' (issued on September 30, 2015), Maruzen Corporation, II-317 See page 321 for more information.
본 발명에 있어서의 산화금속 용해제의 배합량은 적의 선택되지만, 연마액 전체 중량에 대하여, 0.05~3.0중량%인 것이 바람직하고, 0.1~1.0중량%인 것이 보다 바람직하다. 산화금속 용해제의 배합량이 0.05중량% 미만인 경우는, 충분한 연마속도를 얻을 수 없는 경향이 있고, 3.0중량%를 초과하는 경우는, 실용적인 평탄성을 얻을 수 없는 경향이 있다.Although the compounding quantity of the metal oxide dissolving agent in this invention is suitably selected, it is preferable that it is 0.05-3.0 weight% with respect to the polishing liquid total weight, and it is more preferable that it is 0.1-1.0 weight%. When the compounding quantity of the metal oxide solubilizer is less than 0.05% by weight, a sufficient polishing rate tends not to be obtained, and when it exceeds 3.0% by weight, practical flatness tends not to be obtained.
본 발명에 있어서의 금속 방식제는, 금속막 표면의 산화층 상에 보호막을 형성하고, 산화층의 연마액 중에의 용해를 방지하는 것으로 생각되어, 예를 들면, 암모니아; 디메틸아민, 트리메틸아민, 트리에틸아민, 프로필렌디아민 등의 알킬아민이나, 에틸렌디아민테트라아세트산(EDTA), 디에틸디티오카바민산나트륨, 키토산 등의 아민; 디티존, 쿠프로인(2,2'-비퀴놀린), 네오쿠프로인(2,9-디메틸-1,10-페난트롤린), 바소쿠프로인(2,9-디메틸-4,7-디페닐-1,10-페난트롤린), 큐페라존(비스시클로헥사논옥살릴히드라존) 등의 이민; 벤즈이미다졸-2-티올, 트리아진디티올, 트리아진트리티올, 2-[2-(벤조티아졸릴)]티오프로피온산, 2-[2-(벤조티아졸릴)]티오부틸산, 2-멜캅토벤조티아졸, 1,2,3-트리아졸, 1,2,4-트리아졸, 3-아미노-1H-1,2,4-트리아졸, 벤조트리아졸, 1-히드록시벤조트리아졸, 1-디히드록시프로필벤조트리아졸, 2,3-디카르복시프로필벤조트리아졸, 4-히드록시벤조트리아졸, 4-카르복실-1H-벤조트리아졸, 4-카르복실-1H-벤조트리아졸메틸에스테르, 4-카르복실-1H-벤조트리아졸부틸에스테르, 4-카르복실-1H-벤조트리아졸옥틸에스테르, 5-헥실벤조트리아졸, N-(1,2,3-벤조트리아졸릴-1-메틸)-N-(1,2,4-트리아졸릴-1-메틸)-2-에틸헥실아민, 톨릴트리아졸, 나프토트리아졸, 비스[(1-벤조트리아졸릴)메틸]포스폰산 등의 아졸; 노닐멜캅탄, 도데실멜캅탄 등의 멜캅탄; 및 글루코오스, 셀룰로오스, 도데실벤젠술폰산, 도데실황산 및 그 염 등을 들 수 있다. 이들 중에서도 함질소 환상화합물, 이온성 계면활성제가 에칭속도의 억제와 높은 연마속도의 양립에 적합하고, 함질소 환상화합물이 보다 적합하다. 이온성 계면활성제로서는, 이온성기가 술폰산기, 카르본산기, 인산기, 페놀성 수산기의 어느 하나 혹은 복수로 이루어지고, 소수성 기가 탄소수 6 이상으로 이루어지는 이온성 계면활성제가 바람직하다. 이들 금속 방식제는 1종 단독으로, 혹은 2종 이상을 조합시켜서 사용할 수 있다.The metal anticorrosive agent in this invention is considered to form a protective film on the oxide layer of the metal film surface, and to prevent melt | dissolution in the polishing liquid of an oxide layer, For example, Ammonia; Alkylamines such as dimethylamine, trimethylamine, triethylamine, and propylenediamine; amines such as ethylenediaminetetraacetic acid (EDTA), sodium diethyldithiocarbamate, and chitosan; Ditizone, cuproin (2,2'-biquinoline), neocouproin (2,9-dimethyl-1,10-phenanthroline), vasocuproin (2,9-dimethyl-4,7 Imines, such as -diphenyl-1,10-phenanthroline) and cupperazone (biscyclohexanone oxalyl hydrazone); Benzimidazole-2-thiol, triazinedithiol, triazinetriol, 2- [2- (benzothiazolyl)] thiopropionic acid, 2- [2- (benzothiazolyl)] thiobutyl acid, 2-mercapto Benzothiazole, 1,2,3-triazole, 1,2,4-triazole, 3-amino-1H-1,2,4-triazole, benzotriazole, 1-hydroxybenzotriazole, 1 -Dihydroxypropylbenzotriazole, 2,3-dicarboxypropylbenzotriazole, 4-hydroxybenzotriazole, 4-carboxyl-1H-benzotriazole, 4-carboxyl-1H-benzotriazolemethyl Ester, 4-carboxyl-1H-benzotriazole butyl ester, 4-carboxyl-1H-benzotriazole octyl ester, 5-hexylbenzotriazole, N- (1,2,3-benzotriazolyl-1- Methyl) -N- (1,2,4-triazolyl-1-methyl) -2-ethylhexylamine, tolyltriazole, naphthotriazole, bis [(1-benzotriazolyl) methyl] phosphonic acid Azoles; Melcaptans such as nonyl melcaptan and dodecyl melcaptan; And glucose, cellulose, dodecylbenzenesulfonic acid, dodecyl sulfate, and salts thereof. Among these, nitrogen-containing cyclic compounds and ionic surfactants are suitable for both suppressing the etching rate and high polishing rate, and nitrogen-containing cyclic compounds are more suitable. As an ionic surfactant, the ionic surfactant which an ionic group consists of one or more of a sulfonic acid group, a carboxylic acid group, a phosphoric acid group, and a phenolic hydroxyl group is preferable, and a hydrophobic group consists of C6 or more is preferable. These metal anticorrosive agents can be used individually by 1 type or in combination of 2 or more type.
본 발명에 있어서의 금속 방식제의 배합량은 적의 선택되지만, 연마액 전체 중량에 대하여, 0.05~3.0중량%인 것이 바람직하고, 0.1~1.0중량%인 것이 보다 바람직하다. 금속 방식제의 배합량이 0.05중량% 미만인 경우는, 충분한 방식 효과를 얻지 못하고 에칭이 증가하여 평탄성이 악화하는 경향이 있고, 3.0중량%를 초과하는 경우는, 실용적인 연마속도가 얻어지지 않는 경향이 있다.Although the compounding quantity of the metal anticorrosive agent in this invention is suitably selected, it is preferable that it is 0.05-3.0 weight% with respect to the total weight of polishing liquid, and it is more preferable that it is 0.1-1.0 weight%. When the amount of the metal anticorrosive agent is less than 0.05% by weight, sufficient anticorrosive effect is not obtained and the etching tends to increase and the flatness tends to deteriorate. When the amount of the metal anticorrosive agent is more than 3.0% by weight, the practical polishing rate tends not to be obtained. .
본 발명에 있어서의 음이온성 관능기를 가지는 수용성 폴리머의 중량평균분자량은 8,000 이상이고, 바람직하게는 8,000 이상 200,000 이하이며, 보다 바람직하게는 20,000 이상 100,000 이하이며, 특히 바람직하게는 40,000 이상 80,000 이하이다. 중량평균분자량이 8,000 미만인 경우는, 연마속도가 저하하고, 또한, 딧싱이 증가해 버린다. 또한, 중량평균분자량의 상한에 대해서는 특별히 제한이 없지만, 예를 들면, 200,000을 초과하면, 연마속도의 대폭적인 저하는 확인되지 않지만, 연마 웨이퍼면 내의 연마속도 분포의 분산이 커져, 딧싱이 증가하는 경향이 있다.The weight average molecular weight of the water-soluble polymer which has an anionic functional group in this invention is 8,000 or more, Preferably it is 8,000 or more and 200,000 or less, More preferably, it is 20,000 or more and 100,000 or less, Especially preferably, it is 40,000 or more and 80,000 or less. When the weight average molecular weight is less than 8,000, the polishing rate is lowered and the dicing is increased. In addition, there is no restriction | limiting in particular about the upper limit of a weight average molecular weight, For example, when 200,000 is exceeded, the drastic fall of a grinding | polishing speed will not be recognized, but dispersion of the grinding | polishing rate distribution in a grinding | polishing wafer surface becomes large, and dicing increases. There is a tendency.
본 발명에 있어서의 음이온성 관능기를 가지는 수용성 폴리머의 중량평균분자량의 측정은, 겔침투크로마토그래피법으로 실시하였다. 측정조건 등은 이하에 나타내는 바와 같다.The measurement of the weight average molecular weight of the water-soluble polymer which has an anionic functional group in this invention was performed by the gel permeation chromatography method. Measurement conditions are as shown below.
펌프: 주식회사 히다치제작소 제조 L-6000형Pump: Hitachi, Ltd. L-6000 type
검출기: 주식회사 히다치제작소 제조 L-3300형 R1 검출기Detector: L-3300 type R1 detector manufactured by Hitachi Corporation
컬럼: 주식회사 히다치제작소 제조 Gelpack GL-W500Column: Gelpack GL-W500, manufactured by Hitachi Corporation
컬럼 사이즈: 10.7mm(φ)×300mmColumn size: 10.7 mm (φ) × 300 mm
용리액: 100mM 인산 완충액(pH=6.8)/아세토니트릴=90/10(Vol%)
Eluent: 100 mM phosphate buffer (pH = 6.8) / acetonitrile = 90/10 (Vol%)
*액송압력: 17kgf/cm2 * Feeding pressure: 17kgf / cm 2
용리액 유량: 1.0ml/minEluent flow rate: 1.0ml / min
측정 샘플량: 50㎕Sample volume measured: 50 μl
검량선: PEG/PEOCalibration curve: PEG / PEO
음이온성 관능기를 가지는 수용성 폴리머는, 술폰산기, 카르본산기, 인산기, 또는 그 염의 적어도 1종을 가지는 수용성 폴리머이다. 이러한 음이온성 관능기로서는, 술폰산기, 카르본산기, 인산기가 바람직하고, 술폰산기, 카르본산기가 보다 바람직하다. 또한, 염으로서는, 알칼리금속염, 알칼리토류금속염, 할로겐화물, 암모늄염 등이 예시되지만, 연마액을 적용하는 기판이 반도체 집적회로용 실리콘기판 등의 경우는, 알칼리금속, 알칼리토류금속, 할로겐화물 등에 의한 오염은 바람직하지 않기 때문에 암모늄염이 바람직하다. 수용성 폴리머는 이러한 음이온성 관능기를 적어도 1종 가지고 있고, 2종 이상 함유하고 있어도 좋다. 또한, 음이온성 관능기가 다른 수용성 폴리머를 2종 이상 사용할 수 있다.The water-soluble polymer which has an anionic functional group is a water-soluble polymer which has at least 1 sort (s) of a sulfonic acid group, a carboxylic acid group, a phosphoric acid group, or its salt. As such anionic functional group, a sulfonic acid group, a carboxylic acid group, and a phosphoric acid group are preferable, and a sulfonic acid group and a carboxylic acid group are more preferable. Examples of the salt include alkali metal salts, alkaline earth metal salts, halides, ammonium salts, and the like. However, when the substrate to which the polishing liquid is applied is a silicon substrate for semiconductor integrated circuits or the like, alkali metals, alkaline earth metals, halides, etc. may be used. Ammonium salts are preferred because contamination is undesirable. The water-soluble polymer has at least 1 type of such anionic functional group, and may contain 2 or more types. In addition, two or more kinds of water-soluble polymers having different anionic functional groups can be used.
이러한 음이온성기를 가지는 수용성 폴리머로서, 폴리스티렌술폰산, 폴리아크릴아미드메틸프로판술폰산, 폴리사과산, 폴리아크릴산, 폴리메타크릴산, 폴리크로톤산, 폴리이타콘산, 폴리말레인산, 폴리푸말산, 폴리비닐술폰산, 폴리아스파라긴산, 폴리글루타민산, 폴리인산, 폴리메타인산, 또는 그 암모늄염, 알칼리금속염, 알칼리토류금속염 등을 들 수 있다. 이들 중에서도, 폴리카르본산이 상용된다. 또한, 여기서 폴리카르본산이란, 관능기로서 카르복실기를 가지는 수용성 폴리머이다.As the water-soluble polymer having such an anionic group, polystyrene sulfonic acid, polyacrylamide methyl propanesulfonic acid, polyamic acid, polyacrylic acid, polymethacrylic acid, polycrotonic acid, polyitaconic acid, polymaleic acid, polyfumal acid, polyvinylsulfonic acid, poly Aspartic acid, polyglutamic acid, polyphosphoric acid, polymethamic acid or its ammonium salt, alkali metal salt, alkaline earth metal salt, and the like. Among these, polycarboxylic acid is compatible. In addition, polycarboxylic acid is a water-soluble polymer which has a carboxyl group as a functional group here.
이들 음이온성 관능기를 가지는 수용성 폴리머는, 종래법에 근거하여 제조할 수 있다.The water-soluble polymer which has these anionic functional groups can be manufactured based on a conventional method.
본 발명에서는, 음이온성 관능기를 가지는 수용성 폴리머를 첨가함으로써, 높은 연마속도와 양호한 딧싱을 얻을 수 있다. 이러한 수용성 폴리머의 배합량은 적의 선택되지만, 연마액 전체 중량에 대하여, 0.05~2.0중량%인 것이 바람직하고, 0.1~0.8중량%인 것이 보다 바람직하다. 음이온성 관능기를 가지는 수용성 폴리머의 배합량이 0.05중량% 미만인 경우는, 실용적인 연마속도를 얻을 수 없는 경향이 있다. In the present invention, by adding a water-soluble polymer having an anionic functional group, a high polishing rate and good dicing can be obtained. Although the compounding quantity of such a water-soluble polymer is suitably selected, it is preferable that it is 0.05-2.0 weight% with respect to the polishing liquid total weight, and it is more preferable that it is 0.1-0.8 weight%. When the compounding quantity of the water-soluble polymer which has an anionic functional group is less than 0.05 weight%, there exists a tendency for a practical grinding | polishing rate not to be obtained.
도 1에 pH와 음이온성 관능기를 가지는 수용성 폴리머의 입경 및 딧싱의 관계를 나타낸다. 음이온성 관능기를 가지는 수용성 폴리머의 입경은, 음이온성 관능기를 가지는 수용성 폴리머를 산화금속 용해제의 첨가량으로 pH 조정한 것을 측정했다.1 shows the relationship between the particle diameter and the dicing of the water-soluble polymer having a pH and an anionic functional group. The particle size of the water-soluble polymer having an anionic functional group was measured by adjusting the pH of the water-soluble polymer having an anionic functional group by the addition amount of the metal oxide solubilizer.
음이온성 관능기를 가지는 수용성 폴리머는, 폴리카르본산이고, 산화금속 용해제는 황산을 이용했다.The water-soluble polymer having an anionic functional group was polycarboxylic acid and sulfuric acid was used as the metal oxide solubilizer.
금속용 연마액은, 금속의 산화제, 산화금속 용해제, 금속 방식제 및 음이온성 관능기를 가지는 수용성 폴리머를 포함하고, 그 pH는 산화금속 용해제의 첨가량으로 조정했다.The polishing liquid for metals contained the metal oxidizing agent, the metal oxide dissolving agent, the metal anticorrosive agent, and the water-soluble polymer which has an anionic functional group, and the pH was adjusted with the addition amount of the metal oxide dissolving agent.
금속의 산화제는, 과산화수소, 산화금속 용해제는, 황산, 금속 방식제는 벤조트리아졸, 음이온성 관능기를 가지는 수용성 폴리머는 폴리카르본산이다. 또한, 여기서 음이온성 관능기를 가지는 수용성 폴리머의 입경이란, 레이저 회절식 입도분포 합계로 얻어진 값이며, 수용액 중에서의 폴리머쇄의 확장을 나타내는 지침으로서 파악하고 있다. 또한 표시된 입경은 메디안경(median size)이다. pH가 낮아지는 만큼, 폴리머경이 작아지는 것을 알 수 있다. 이것은 pH가 낮아지면 음이온성 관능기의 해리가 억제되어 음이온성 관능기 사이의 정전반발이 저하하여 폴리머쇄가 수축하였기 때문이라고 생각하고 있다. 또한, pH가 낮아짐에 따라 딧싱이 억제 되고 있는 것을 알 수 있다.The metal oxidant is hydrogen peroxide, the metal oxide solubilizer, sulfuric acid, the metal anticorrosive agent is benzotriazole, and the water-soluble polymer having an anionic functional group is polycarboxylic acid. In addition, the particle diameter of the water-soluble polymer which has an anionic functional group is a value obtained by the sum total of a laser diffraction particle size distribution, and grasped | ascertained as a guide | line which shows expansion of a polymer chain in aqueous solution. Also shown is the median size (median size). It turns out that polymer diameter becomes small, so that pH becomes low. It is thought that this is because dissociation of the anionic functional group is suppressed when the pH is lowered, and the electrostatic repulsion between the anionic functional groups is reduced to shrink the polymer chain. Moreover, it turns out that dicing is suppressed as pH becomes low.
피연마 금속 상에 형성되는 보호막은, 금속 연마액 중의 금속 방식제나 폴리머의 흡착층 또는 금속 방식제나 폴리머와 피연마 금속 혹은 그 이온이 배위결합, 이온결합, 공유결합 등에 의해서 결합한 반응물의 층으로 생각된다.The protective film formed on the polished metal is regarded as a layer of a metal anticorrosive agent or polymer in the metal polishing liquid or a layer of a reactant in which the metal anticorrosive agent or polymer and the polymer to be polished or their ions are bonded by coordination bonds, ionic bonds, and covalent bonds. do.
금속 방식제는, 치밀한 또한 강고한 보호막을 형성하기 위해 딧싱 억제에는 매우 효과적이지만, 첨가량의 증가에 의해서 연마속도를 저하시킨다. 한편, 수용성 폴리머를 첨가한 금속용 연마액으로는, 연마속도의 저하를 회피할 수 있지만, 딧싱의 증가 억제효과가 저감한다. 이것은, 금속용 연마액 중에서 수용성의 폴리머쇄가 신장상태로 존재하고, 이 폴리머쇄에 의해서 형성된 보호막은 조잡한 보호막이 되고, 이것이 딧싱의 증가 억압효과를 저하시키고 있다고 생각된다.The metal anticorrosive is very effective in suppressing the dicing in order to form a dense and firm protective film, but the polishing rate is lowered by increasing the amount added. On the other hand, with the polishing liquid for metals to which the water-soluble polymer was added, the fall of a polishing rate can be avoided, but the suppression effect of an increase of a dicing decreases. This is considered to be that the water-soluble polymer chain is present in the elongated state in the polishing liquid for metal, and the protective film formed by the polymer chain becomes a coarse protective film, which lowers the increase suppressing effect of the dicing.
본 발명의 금속용 연마액은, 저pH 영역을 이용하는 것으로 폴리머쇄가 수축한 수용성 폴리머, 즉 치밀한 수용성 폴리머가 피연마 금속상을 효율적으로 피복 함으로써 치밀한 보호막을 형성하여 딧싱의 증가를 억제하는 것으로 생각되고 있다. 일반적으로 폴리머의 분자량이 큰 것은 연마속도는 빨라지지만, 피연마면의 평탄성을 얻기 어려워지고, 반대로 폴리머의 분자량이 작은 것은 피연마면의 평탄성은 얻을 수 있지만 연마속도가 늦어지는 경향이 있다. 본 발명에서는 중량평균분자량 8000 이상의 수용성 폴리머를 이용하여 특정의 pH 영역으로 설정함으로써, 수용성 폴리머의 폴리머쇄가 수축하여 폴리머 입경이 작아지는 것으로 생각되고, 그 결과, 고연마속도와 피연마면의 평탄성을 달성할 수 있다. 또한 금속 방식제와 같은 강고한 보호막이 아니고, 치밀하기는 하지만 연질인 보호막을 형성하는 것으로 높은 연마속도를 얻는 것으로 생각되고 있다. 일반적으로 금속 방식제와 수용성 폴리머를 병용함으로써, 금속 방식제 단독 사용에 비해 연질인 보호막이 형성되어 연마속도는 향상하지만, 피연마면의 평탄성이 얻어지지는 않는다. 본 발명에서는 금속 방식제와 중량평균분자량 8000 이상의 수용성 폴리머를 이용하여 특정의 pH 영역으로 설정함으로써, 고연마속도와 피연마면의 평탄성을 달성할 수 있다.The metal polishing liquid of the present invention uses a low pH region, and a water-soluble polymer in which the polymer chain is shrunk, that is, a dense water-soluble polymer effectively forms a dense protective film by suppressing an increase in dicing by coating the polished metal phase efficiently. It is becoming. Generally, the higher the molecular weight of the polymer, the faster the polishing rate is, but the flatness of the polished surface becomes difficult. On the contrary, the lower the molecular weight of the polymer is, the smoother the polishing surface is, but the polishing rate tends to be slower. In the present invention, by setting the specific pH range using a water-soluble polymer having a weight average molecular weight of 8000 or more, it is considered that the polymer chain of the water-soluble polymer shrinks and the polymer particle size is reduced. As a result, high polishing speed and flatness of the surface to be polished are obtained. Can be achieved. In addition, it is thought that a high polishing rate is obtained by forming a dense but soft protective film rather than a hard protective film such as a metal anticorrosive. Generally, by using a metal anticorrosive agent and a water-soluble polymer together, a soft protective film is formed compared with the use of a metal anticorrosive agent alone, and a polishing rate improves, but the flatness of a to-be-polished surface is not obtained. In the present invention, by setting the specific pH range using a metal anticorrosive and a water-soluble polymer having a weight average molecular weight of 8000 or more, it is possible to achieve high polishing rate and flatness of the surface to be polished.
(수용성 (receptivity 폴리머Polymer 입경 측정방법) Particle size measurement method)
본 발명에서 사용되는 산화금속 용해제로 pH를 조정한 수용액 중의 수용성 폴리머의 입경(실시예에서는 메디안경으로 기재한다.)을, 레이저 회절식 입도분포계로 측정했다.The particle size of the water-soluble polymer in the aqueous solution whose pH was adjusted with the metal oxide solubilizer used in the present invention (in the Examples, described as a median glasses) was measured by a laser diffraction particle size distribution system.
측정장치: MALVERN사 제조 ZETASIZER3000HSMeasuring device: ZETASIZER3000HS manufactured by MALVERN
측정 조건: 온도 25℃Measuring condition:
분산매의 굴절율 1.33 Refractive index of the dispersion medium 1.33
분산매의 점도 0.89cP Viscosity of Dispersion Medium 0.89 cP
본 발명에서는, 금속용 연마액에 연마입자를 첨가해도 좋고, 연마입자를 첨가함으로써 연마속도를 더 향상시킬 수 있다. 다만, 연마입자를 첨가함으로써 딧싱이 증가하는 가능성이 있기 때문에, 연마입자의 첨가량은 본 발명의 효과에 영향을 미치지 않는 범위에서 적의 선택된다. 연마입자의 첨가량은, 연마액 중량에 대하여, 1중량% 미만이 바람직하고, 0.001~1중량%가 보다 바람직하고, 0.03~1중량%가 특히 바람직하다. 연마입자의 첨가량이 1중량%를 초과하면 딧싱이 악화하는 경향이 있다. 연마입자의 첨가량의 하한은 특별히 제한되지 않지만, 예를 들면, 0.001중량% 미만이면 연마속도의 향상에 기여하지 않고 첨가하는 효과가 나타나지 않는 경향이 있다.In the present invention, the abrasive grains may be added to the polishing liquid for metal, and the polishing rate can be further improved by adding the abrasive grains. However, since there is a possibility that the dicing increases by adding the abrasive grains, the addition amount of the abrasive grains is appropriately selected within a range that does not affect the effect of the present invention. The addition amount of the abrasive grains is preferably less than 1% by weight, more preferably 0.001 to 1% by weight, particularly preferably 0.03 to 1% by weight based on the weight of the polishing liquid. When the amount of the abrasive grains added exceeds 1% by weight, the dicing tends to deteriorate. The lower limit of the addition amount of the abrasive grains is not particularly limited, but, for example, if the amount is less than 0.001% by weight, the effect of addition without contributing to the improvement of the polishing rate tends not to appear.
연마입자로서는, 예를 들면, 실리카, 알루미나, 티타니아, 세리아, 지르코니아, 또한 게르마니아 등의 무기물지립, 폴리스티렌, 폴리아크릴, 폴리염화비닐 등의 유기 연마입자 등을 들 수 있고, 이들 중에서도 실리카, 알루미나, 세리아가 바람직하고, 콜로이달실리카 및/또는 콜로이달실리카류가 보다 바람직하다. 또한 상기 연마입자에 미량 금속종의 첨가나, 표면 수식을 실시하고, 전위를 조정한 것을 사용할 수도 있다. 그 방법에 특별히 제한은 없다. 여기서, 콜로이달실리카류는 콜로이달실리카를 기초로 하여, 졸·겔 반응시에 있어서 금속종을 미량 첨가한 것, 표면 실라놀기에 화학 수식 등을 실시한 것 등을 가리키고, 그 방법에 특별히 제한은 없다. 이들 연마입자는 1종류 단독으로, 혹은 2종 이상을 조합시켜서 사용할 수 있다.Examples of the abrasive particles include silica, alumina, titania, ceria, zirconia, and inorganic abrasive grains such as germania, organic abrasive particles such as polystyrene, polyacryl, polyvinyl chloride, and the like. Among these, silica, alumina, Ceria is preferable, and colloidal silica and / or colloidal silica are more preferable. Moreover, addition of a trace metal species, surface modification, and adjustment of dislocation can also be used for the said abrasive grain. There is no restriction | limiting in particular in the method. Here, colloidal silicas refer to the addition of a trace amount of metal species in the sol-gel reaction, the chemical modification of the surface silanol group, etc. on the basis of colloidal silica, and the method is not particularly limited. none. These abrasive particles can be used individually by 1 type or in combination of 2 or more types.
연마입자의 일차 입자경은, 피연마 금속의 종류나 연마입자의 종류 등에 따라 적의 조정되지만, 바람직하게는 200nm 이하, 보다 바람직하게는 5~200nm, 특히 바람직하게는 5~150nm, 매우 바람직하게는 5~100nm이다. 일차 입자경이 200nm를 초과하면, 연마면의 평탄성이 악화하는 경향이 있다. 또한 5nm 미만의 일차 입자경을 선택하는 경우는, CMP 속도가 낮아지는 가능성이 있으므로 주의가 필요하다.The primary particle size of the abrasive particles is suitably adjusted according to the kind of the polished metal, the kind of the abrasive grain, etc., but is preferably 200 nm or less, more preferably 5 to 200 nm, particularly preferably 5 to 150 nm, and very preferably 5 ˜100 nm. When the primary particle size exceeds 200 nm, the flatness of the polished surface tends to deteriorate. In addition, when selecting the primary particle diameter of less than 5 nm, care should be taken because the CMP rate may be lowered.
또한, 연마입자가 회합하고 있는 경우, 이차 입자경은, 바람직하게는 200nm 이하, 보다 바람직하게는 10~200nm, 특히 바람직하게는 10~150nm, 매우 바람직하게는 10~100nm이다. 이차 입자경이 200nm를 초과하면, 연마면의 평탄성이 악화하는 경향이 있다. 또한 10nm 미만인 이차 입자경을 선택하는 경우는, 연마입자에 의한 메카니컬적인 반응층 제거 능력이 불충분해져 CMP 속도가 낮아지는 가능성이 있으므로 주의가 필요하다.In addition, when the abrasive grains associate, the secondary particle diameter is preferably 200 nm or less, more preferably 10 to 200 nm, particularly preferably 10 to 150 nm, and very preferably 10 to 100 nm. When the secondary particle size exceeds 200 nm, the flatness of the polished surface tends to deteriorate. In the case of selecting a secondary particle size of less than 10 nm, care should be taken because the ability to remove the mechanical reaction layer by the abrasive particles may be insufficient and the CMP rate may be lowered.
본 발명에 있어서의 연마입자의 일차 입자경은, 투과형 전자현미경(예를 들면, 주식회사 히다치제작소 제조의 S4700)을 이용하여 측정할 수 있다. 또한, 이차 입자경은, 광회절 산란식 입도분포계(예를 들면, COULTER EIectronics사 제조의 COULTER N4SD)를 이용하여 측정할 수 있다.The primary particle diameter of the abrasive grain in this invention can be measured using a transmission electron microscope (For example, S4700 by the Hitachi Corporation make). In addition, a secondary particle diameter can be measured using an optical diffraction scattering particle size distribution system (for example, COULTER N4SD by COULTER EIectronics).
본 발명의 금속용 연마액은, 상술한 성분 외에, 염료, 안료 등의 착색제나, pH 조정제, 물 이외의 용매 등의, 일반적으로 연마액에 첨가되는 첨가제를, 연마액의 작용효과를 손상시키지 않는 범위에서 첨가해도 좋다.The polishing liquid for metals of the present invention, in addition to the above-described components, additives generally added to the polishing liquid, such as colorants such as dyes and pigments, pH adjusters, and solvents other than water, do not impair the effect of the polishing liquid. You may add in the range which does not.
본 발명의 피연마막의 연마 방법은, 연마정반의 연마포 상에 상기 본 발명의 금속용 연마액을 공급하면서, 피연마 금속막을 가지는 기판을 연마포에 압압한 상태로 연마정반과 기판을 상대적으로 작동시켜 피연마 금속막을 연마하는 것을 특징으로 한다.In the polishing method of the polished film of the present invention, while polishing the substrate having the polished metal film on the polishing cloth while supplying the polishing liquid for metal of the present invention onto the polishing cloth of the polishing table, the polishing plate and the substrate are relatively It is characterized by grinding | polishing the to-be-polished metal film | membrane by operation.
연마 대상인 피연마 금속막은 단층이라도 적층이라도 상관없다. 금속막으로서는, 구리, 알루미늄, 텅스텐, 탄탈륨, 티타늄 등의 금속, 그들의 금속의 합금, 그들 금속 또는 금속합금의 산화물이나 질화물 등의 화합물의 어느 1종 이상이 예시된다. 이들 중에서도, 구리, 구리합금, 구리화합물이 바람직하다. 금속막은 스퍼터법이나 도금법 등의 공지된 방법에 의해 성막된다. 기판으로서는, 반도체장치 제조에 관한 기판, 예를 들면 회로소자와 배선패턴이 형성된 단계의 반도체 기판, 회로소자가 형성된 단계의 반도체 기판 등의 반도체 기판 상에, 절연층이 형성된 기판 등을 들 수 있다. The polished metal film to be polished may be a single layer or a lamination. As a metal film, any 1 or more types of compounds, such as metals, such as copper, aluminum, tungsten, tantalum, and titanium, alloys of these metals, oxides and nitrides of these metals or metal alloys, are illustrated. Among these, copper, a copper alloy, and a copper compound are preferable. The metal film is formed by a known method such as sputtering or plating. As a board | substrate which concerns on semiconductor device manufacture, for example, the semiconductor substrate of the stage in which the circuit element and the wiring pattern were formed, the semiconductor substrate, such as the semiconductor substrate of the stage in which the circuit element was formed, etc. are mentioned. .
본 발명의 연마 방법에 있어서 사용할 수 있는 연마 장치로서는, 예를 들면, 피연마 금속막을 가지는 기판을 보관 유지하는 홀더와 연마포(패드)를 붙일 수 있고, 회전수가 변경 가능한 모터 등을 설치하고 있는 연마정반을 가지는 일반적인 연마 장치가 사용될 수 있다. 예를 들면, 아프라이드머테리얼즈사 제조 MIRRA가 사용될 수 있다.As the polishing apparatus which can be used in the polishing method of the present invention, for example, a holder for holding a substrate having a to-be-polished metal film and a polishing cloth (pad) can be attached to each other, and a rotating motor can be provided. A general polishing apparatus having a polishing table can be used. For example, MIRRA manufactured by Apride Materials can be used.
연마정반 상의 연마포로서는, 특별히 제한이 없고, 일반적인 부직포, 발포 폴리우레탄, 다공질 플루오로수지 등이 사용될 수 있다. 연마 조건은, 특별히 제한이 없지만, 기판이 튀어나오지 않도록 정반의 회전속도를 200rpm 이하의 저회전으로 하는 것이 바람직하다.There is no restriction | limiting in particular as a polishing cloth on a polishing plate, A general nonwoven fabric, a foamed polyurethane, a porous fluororesin etc. can be used. The polishing conditions are not particularly limited, but it is preferable that the rotational speed of the surface plate is set at a low rotation of 200 rpm or less so that the substrate does not protrude.
피연마 금속막을 가지는 기판의 연마포에의 연마 압력은 5~100kPa인 것이 바람직하고, 연마속도의 피연마 금속막면 내의 균일성 및 패턴의 평탄성의 견지로부터 10~50kPa인 것이 바람직하다.It is preferable that the polishing pressure of the board | substrate which has a to-be-polished metal film to a polishing cloth is 5-100 kPa, and it is preferable that it is 10-50 kPa from the viewpoint of the uniformity in the to-be-polished metal film surface of a polishing rate, and flatness of a pattern.
기판의 피연마 금속막을 연마포에 압압한 상태로 연마포와 피연마 금속막을 상대적으로 작동시키려면, 구체적으로는 기판과 연마정반의 적어도 하나를 작동시키면 된다. 연마정반을 회전시키는 것 외에, 홀더를 회전이나 요동시켜서 연마해도 좋다. 또한, 연마정반을 유성 회전시키는 연마 방법, 벨트 상태의 연마포를 긴 방향의 한쪽 방향에 직선 상태로 작동시키는 연마 방법 등을 들 수 있다. 또한 홀더는 고정, 회전, 요동의 어느 상태라도 좋다. 이들 연마 방법은, 연마포와 피연마 금속막을 상대적으로 작동시키는 것이면, 피연마면이나 연마 장치에 의해 적의 선택할 수 있다.Specifically, at least one of the substrate and the polishing plate may be operated to relatively operate the polishing cloth and the polished metal film while the substrate to be polished is pressed against the polishing cloth. In addition to rotating the polishing platen, the holder may be rotated or rocked to polish. Moreover, the grinding | polishing method of planetary rotation of a polishing table, the grinding | polishing method of operating the grinding | polishing cloth of a belt state in a linear state to one direction of a long direction, etc. are mentioned. The holder may be in any of the states of fixing, rotation, and swinging. These polishing methods can be suitably selected by the surface to be polished or the polishing apparatus as long as the polishing cloth and the to-be-polished metal film are relatively operated.
연마하고 있는 동안, 연마포에는 금속용 연마액을 펌프 등으로 연속적으로 공급하는 것이 바람직하다. 이 공급량에 제한은 없지만, 연마포의 표면이 항상 연마액으로 덮여 있는 것이 바람직하다. 구체적으로는, 연마포 면적 1cm2 당, 0.3~0.9밀리리터로 공급되는 것이 바람직하다.While polishing, it is preferable to continuously supply a polishing liquid for metal to the polishing cloth by a pump or the like. Although this supply amount is not limited, it is preferable that the surface of the polishing cloth is always covered with the polishing liquid. Specifically, it is preferable to supply 0.3-0.9 milliliters per 1 cm <2> of polishing cloth areas.
연마 종료 후의 반도체 기판은, 유수 중에서 잘 세정 후, 스핀 드라이어 등을 이용하여 반도체 기판 상에 부착한 수적을 닦아내고 나서 건조시키는 것이 바람직하다.It is preferable to dry a semiconductor substrate after completion | finish of grinding | polishing after wash | cleaning well in flowing water, after wiping off the water droplets adhering on a semiconductor substrate using a spin dryer etc.
본 발명의 금속용 연마액 및 피연마막의 연마 방법에 의하면, 상기 (a)~(d)의 문제를 해결할 수 있고, 또한 높은 연마속도로 낮은 딧싱, 즉 테크놀러지 노드 130nm 이후에 필요하게 되는 레벨의 매입 Cu 배선을 형성할 수 있다.According to the polishing method of the metal polishing liquid and the polished film of the present invention, the problems of (a) to (d) can be solved, and at a high polishing rate, the level required after low dicing, that is, after the technology node 130 nm Embedded Cu wiring can be formed.
[도 1] 도 1은, 음이온성 관능기를 가지는 수용성 폴리머가 폴리카르본산이고, 산화금속 용해제가 황산인 수용액의 pH와 폴리머경의 관계 및 금속의 산화제가 과산화수소, 산화금속 용해제가 황산, 금속 방식제가 벤조트리아졸, 음이온성 관능기를 가지는 수용성 폴리머가 폴리카르본산인 금속용 연마액의 pH와 딧싱의 관계로 플롯한 그래프이다.1 shows a relationship between the pH and the polymer diameter of an aqueous solution in which a water-soluble polymer having an anionic functional group is polycarboxylic acid, and the metal oxide solubilizer is sulfuric acid, and the metal oxidant is hydrogen peroxide, the metal oxide solubilizer is sulfuric acid, and the metal anticorrosive agent is It is a graph plotted in relation to pH and dicing of the polishing liquid for metals in which a water-soluble polymer having benzotriazole and an anionic functional group is polycarboxylic acid.
이하, 실시예에 의해 본 발명을 설명한다. 본 발명은 이들 실시예에 의해 제한하는 것은 아니다.Hereinafter, the present invention will be described by way of examples. The present invention is not limited by these examples.
(금속용 연마액의 제작)(Production of polishing liquid for metal)
실시예Example 1~6 및 1-6 and 비교예Comparative example 1~2 1-2
연마액 중량에 대하여, 과산화수소수(시약특급, 30% 수용액) 30중량%, 표 1에 나타내는 산화금속 용해제, 벤조트리아졸 0.4중량%, 표 1에 나타내는 음이온성 관능기를 가지는 수용성 폴리머 0.4중량%, 합계 100중량%가 되도록 잔부에 순수를 배합하고, 실시예 1~6의 연마액 (A)~(F) 및 비교예 1~2의 연마액 (I)~(J)를 제작했다. 또한, 연마액의 pH는, 산화금속 용해제의 첨가량으로 표 1에 나타내는 값이 되도록 조정했다.30 weight% of hydrogen peroxide (reagent express, 30% aqueous solution) with respect to the weight of polishing liquid, 0.4 weight% of water-soluble polymers which have a metal oxide solubilizer shown in Table 1, 0.4 weight% of benzotriazole, and an anionic functional group shown in Table 1, Pure water was mix | blended with remainder so that it might be 100 weight% in total, and polishing liquids (A)-(F) of Examples 1-6 and polishing liquids (I)-(J) of Comparative Examples 1-2 were produced. In addition, pH of polishing liquid was adjusted so that it might become a value shown in Table 1 by the addition amount of a metal oxide dissolving agent.
실시예Example 7~8 및 7-8 and 비교예Comparative example 3 3
연마액 중량에 대하여, 과산화수소수(시약특급, 30% 수용액) 30중량%, 표 1에 나타내는 산화금속 용해제, 벤조트리아졸 0.4중량%, 표 1에 나타내는 음이온성 관능기를 가지는 수용성 폴리머 0.4중량%, 메디안경이 60nm인 콜로이달실리카지립 0.05중량%, 합계 100중량%가 되도록 잔부에, 순수를 배합하여 실시예 7~8의 연마액(G)~(H) 및 비교예 3의 연마액(K)을 제작했다. 또한, 연마액의 pH는, 산화금속 용해제의 첨가량으로 표 1에 나타내는 값이 되도록 조정했다.30 weight% of hydrogen peroxide (reagent express, 30% aqueous solution) with respect to the weight of polishing liquid, 0.4 weight% of water-soluble polymers which have a metal oxide solubilizer shown in Table 1, 0.4 weight% of benzotriazole, and an anionic functional group shown in Table 1, Pure water was added to the remainder so that the median glasses had 60% of colloidal silica grains of 100 nm and 100% by weight in total, and the polishing liquids (G) to (H) of Examples 7 to 8 and the polishing liquid (K) of Comparative Example 3 ) In addition, pH of polishing liquid was adjusted so that it might become a value shown in Table 1 by the addition amount of a metal oxide dissolving agent.
비교예Comparative example 4 4
연마액 중량에 대하여, 과산화수소수(시약특급, 30% 수용액) 30중량%, 표 1에 나타내는 산화금속 용해제, 벤조트리아졸 0.4중량%, 합계 100중량%가 되도록 잔부에 순수를 배합하여, 비교예 4의 연마액(L)을 제작했다. 또한, 연마액의 pH는, 산화금속 용해제의 첨가량으로 표 1에 나타내는 값이 되도록 조정했다.With respect to the weight of the polishing liquid, pure water was added to the remainder so that 30% by weight of hydrogen peroxide solution (specialized reagent, 30% aqueous solution), the metal oxide solubilizer shown in Table 1, 0.4% by weight of benzotriazole, and 100% by weight in total were compared. 4 polishing liquids L were produced. In addition, pH of polishing liquid was adjusted so that it might become a value shown in Table 1 by the addition amount of a metal oxide dissolving agent.
비교예Comparative example 5 5
연마액 중량에 대하여, 과산화수소수(시약특급, 30% 수용액) 30중량%, 표 1에 나타내는 산화금속 용해제, 벤조트리아졸 0.4중량%, 표 1에 나타내는 수용성 폴리머(양이온성 폴리머인 폴리리진) 0.4중량%, 합계 100중량%가 되도록 잔부에 순수를 배합하여, 비교예 5의 연마액(M)을 제작했다. 또한, 연마액의 pH는, 산화금속 용해제의 첨가량으로 표 1에 나타내는 값이 되도록 조정했다.30 wt% of hydrogen peroxide (reagent express, 30% aqueous solution), metal oxide solubilizer shown in Table 1, 0.4 wt% of benzotriazole, and water-soluble polymer shown in Table 1 with respect to the weight of the polishing liquid 0.4 Pure water was mix | blended with remainder so that it might become 100 weight% in total, and the polishing liquid M of the comparative example 5 was produced. In addition, pH of polishing liquid was adjusted so that it might become a value shown in Table 1 by the addition amount of a metal oxide dissolving agent.
비교예Comparative example 6 6
연마액 중량에 대하여, 과산화수소수(시약특급, 30% 수용액) 30중량%, 표 1에 나타내는 산화금속 용해제, 벤조트리아졸 0.4중량%, 표 1에 나타내는 수용성 폴리머 0.4중량%, 합계 100중량%가 되도록 잔부에 순수를 배합하고, 비교예 6의 연마액(N)을 제작했다. 또한, 연마액의 pH는, 산화금속 용해제의 첨가량으로 표 1에 나타내는 값이 되도록 조정했다.To the weight of the polishing liquid, 30% by weight of hydrogen peroxide (reagent express, 30% aqueous solution), metal oxide solubilizer shown in Table 1, 0.4% by weight of benzotriazole, 0.4% by weight of water-soluble polymer shown in Table 1, and 100% by weight in total Pure water was mix | blended with the remainder as much as possible, and the polishing liquid N of the comparative example 6 was produced. In addition, pH of polishing liquid was adjusted so that it might become a value shown in Table 1 by the addition amount of a metal oxide dissolving agent.
(구리 배선이 형성된 (Copper wiring formed 피연마용For polishing 기판) Board)
패턴 없는 실리콘기판: 실리콘기판 표면에, 이산화규소 절연막층을 제작하고, 스퍼터법에 의해 15nm의 TaN막과 10nm의 Ta막과 100nm의 구리막을 형성한 후, 상기 분해 도금법에 의해 1.3㎛의 구리를 퇴적한 피연마용 기판을 이용했다.Silicon substrate without pattern: A silicon dioxide insulating film layer was fabricated on the surface of the silicon substrate, a 15 nm TaN film, a 10 nm Ta film, and a 100 nm copper film were formed by the sputtering method, and then 1.3 µm of copper was formed by the decomposition plating method. The deposited substrate for polishing was used.
패턴 부착 실리콘기판: 실리콘기판 표면에, 이산화규소 절연막층을 성막하고, SEMATECH854 마스크패턴으로 이산화규소 절연막층에 배선구를 형성한 후, 스퍼터법에 의해 15nm의 TaN막과 10nm의 Ta막과 100nm의 구리막을 형성하고, 분해 도금법에 의해 1.1㎛의 구리를 퇴적한 피연마용 기판을 이용했다. 또한, 배선구의 깊이는 500nm이다.Silicon substrate with a pattern: A silicon dioxide insulating film layer is formed on the surface of the silicon substrate, a wiring hole is formed in the silicon dioxide insulating film layer with a SEMATECH854 mask pattern, and then a 15 nm TaN film, a 10 nm Ta film and a 100 nm film are formed by a sputtering method. The copper film was formed and the to-be-polished board | substrate which deposited 1.1 micrometers copper by the decomposition plating method was used. In addition, the wiring hole has a depth of 500 nm.
(( CMPCMP 연마조건) Polishing condition)
연마 장치: 아프라이드머테리얼스사 제조 MIRRAPolishing apparatus: MIRRA manufactured by Apride Materials
연마 압력: 13.8kPaPolishing pressure: 13.8kPa
연마액 공급량: 200ml/분Polishing fluid supply amount: 200ml / min
(( CMPCMP 후 세정)Post-cleaning)
CMP 처리 후는, 폴리비닐알코올 제 브러쉬, 초음파수에 의한 세정을 실시한 후, 스핀 드라이어로 건조를 실시했다.After the CMP treatment, after washing with a polyvinyl alcohol brush and ultrasonic water, drying was performed with a spin dryer.
(( 연마품Abrasive 평가 항목) Evaluation item)
구리 연마속도: 상기에서 제작한 각 연마액(A)~(N)을 연마포 상에 공급하면서 상기 패턴 없는 실리콘기판을 상기 연마 조건에 의해 60초간 연마했다. 연마 전후에서의 구리막 두께 차이를 상기 저항값으로부터 환산하여 구했다. 결과를 표 1에 나타낸다.Copper polishing rate: The said silicon pattern-free substrate was polished for 60 seconds by the said grinding | polishing conditions, supplying each polishing liquid (A)-(N) produced above on a polishing cloth. The copper film thickness difference before and after grinding | polishing was calculated | required in conversion from the said resistance value. The results are shown in Table 1.
딧싱량: 상기에서 제작한 각 연마액(A)~(N)을 연마포 상에 공급하면서 상기 패턴 부착 실리콘기판을 상기 연마 조건에 따라 연마했다. 또한 연마는 웨이퍼상으로부터 잉여의 구리가 완전히 제거되고 나서 오버 연마(추가 연마)로서 30초 실시하였다. 접촉식 단차계(Veeco제 DECKTAK V200-Si)를 이용하여, 절연막부에 대한 배선 금속부의 막 감량을 구했다. 결과를 표 1에 나타낸다.Dicing amount: The said silicon substrate with a pattern was polished according to the said polishing conditions, supplying each polishing liquid (A)-(N) produced above on a polishing cloth. The polishing was carried out for 30 seconds as over polishing (additional polishing) after excess copper was completely removed from the wafer. The film loss of the wiring metal part with respect to the insulating film part was calculated | required using the contact type | step type meter (DECKTAK V200-Si made from Veeco). The results are shown in Table 1.
또한, CMP 처리 후의 기판의 시각적 점검, 광학현미경 관찰 및 전자현미경 관찰에 의해 연마 손상 발생의 유무를 확인했다. 그 결과, 모든 실시예 및 비교예에 있어서 현저한 연마 손상의 발생은 확인되지 않았다.In addition, the presence of polishing damage was confirmed by visual inspection of the substrate after the CMP treatment, optical microscope observation, and electron microscope observation. As a result, the occurrence of significant polishing damage was not confirmed in all the examples and the comparative examples.
[표 1][Table 1]
표 1에 나타낸 바와 같이, pH가 3.5인 비교예 1의 연마액(I)은, pH가 2.2인 실시예 1의 연마액(A) 또는 pH가 2.7인 실시예 2의 연마액(B)과 비교하여 딧싱량이 큰 것을 알았다. 또한, pH가 3.5인 비교예 2의 연마액(J)은, pH가 2.2인 실시예 3의 연마액(C) 또는 pH가 2.7인 실시예 4의 연마액(D)과 비교해서 딧싱량이 큰 것을 알았다. 또한, 수용성 폴리머의 중량평균분자량이 7000으로 적은 비교예 3의 연마액(K)은, 수용성 폴리머의 중량평균분자량이 큰 실시예 7의 연마액(G) 또는 실시예(8)의 연마액(H)과 비교해서 연마속도가 낮고 딧싱량도 큰 것을 알았다. 또한, pH가 2.2이고 수용성 폴리머를 이용하지 않은 비교예 4의 연마액(L)은 연마속도가 늦고 딧싱량도 큰 것을 알았다. 또한, 양이온성 폴리머를 이용한 비교예 5의 연마액(M)은 연마속도가 늦고 딧싱량도 큰 것을 알았다. 또한, 수용성 폴리머의 중량평균분자량이 7000으로 적은 비교예 6의 연마액(N)은 연마속도가 늦고 딧싱량도 큰 것을 알았다.As shown in Table 1, the polishing liquid (I) of Comparative Example 1 having a pH of 3.5 is the polishing liquid (A) of Example 1 having a pH of 2.2 or the polishing liquid (B) of Example 2 having a pH of 2.7. In comparison, it was found that the amount of dicing was large. In addition, the polishing liquid J of Comparative Example 2 having a pH of 3.5 has a large amount of dicing compared with the polishing liquid C of Example 3 having a pH of 2.2 or the polishing liquid D of Example 4 having a pH of 2.7. I knew that. In addition, the polishing liquid K of Comparative Example 3 having a low weight average molecular weight of the water-soluble polymer of 7000 is the polishing liquid G of Example 7 or the polishing liquid of Example (8) having a large weight average molecular weight of the water-soluble polymer ( Compared with H), it was found that the polishing rate was low and the amount of dicing was large. In addition, it was found that the polishing liquid L of Comparative Example 4, which had a pH of 2.2 and did not use a water-soluble polymer, had a low polishing rate and a large amount of dicing. In addition, it was found that the polishing liquid M of Comparative Example 5 using the cationic polymer had a slow polishing rate and a large amount of dicing. In addition, it was found that the polishing liquid N of Comparative Example 6 having a low weight average molecular weight of the water-soluble polymer of 7000 had a low polishing rate and a large amount of dicing.
이것에 대해, 실시예 1~8의 연마액(A)~(H)은 연마속도가 높고, 딧싱량이 작은 것을 알았다.On the other hand, it was found that the polishing liquids (A) to (H) of Examples 1 to 8 had a high polishing rate and a small amount of dicing.
Claims (20)
상기 산화금속 용해제가, 25℃에 있어서의 제 1단의 산해리지수가 3.7 미만인 무기산, 유기산 및 이들의 염으로 이루어지는 군으로부터 선택되는 1종 이상의 산화금속 용해제이고,
상기 수용성 폴리머는, 레이저 회절식 입도분포계로 측정되는 입자의 메디안경(median size)이 20nm이하이고,
pH가 1 이상 3 이하인 것을 특징으로 하는 금속용 연마액. Metal oxidizing agent, metal oxide dissolving agent, metal anticorrosive agent and water-soluble polymer having an anionic functional group having a weight average molecular weight of 8,000 to 200,000,
The metal oxide solubilizer is at least one metal oxide solubilizer selected from the group consisting of inorganic acids, organic acids and salts thereof having an acid dissociation number of less than 3.7 at 25 ° C.,
The water-soluble polymer has a median size of particles of 20 nm or less measured by a laser diffraction particle size distribution meter,
pH is 1 or more and 3 or less, The polishing liquid for metals characterized by the above-mentioned.
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| Application Number | Priority Date | Filing Date | Title |
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| JP2005374753 | 2005-12-27 | ||
| JPJP-P-2005-374753 | 2005-12-27 | ||
| PCT/JP2006/326106 WO2007077886A1 (en) | 2005-12-27 | 2006-12-27 | Metal polishing liquid and method for polishing film to be polished |
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| KR1020087014873A Division KR20080070074A (en) | 2005-12-27 | 2006-12-27 | Metal polishing liquid and method for polishing film to be polished |
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| KR20110048563A KR20110048563A (en) | 2011-05-11 |
| KR101260597B1 true KR101260597B1 (en) | 2013-05-06 |
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| KR1020117006918A KR101260597B1 (en) | 2005-12-27 | 2006-12-27 | Metal polishing liquid and method for polishing film to be polished |
| KR1020087014873A KR20080070074A (en) | 2005-12-27 | 2006-12-27 | Metal polishing liquid and method for polishing film to be polished |
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| KR1020087014873A KR20080070074A (en) | 2005-12-27 | 2006-12-27 | Metal polishing liquid and method for polishing film to be polished |
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| Country | Link |
|---|---|
| US (1) | US8791019B2 (en) |
| JP (2) | JP4952584B2 (en) |
| KR (2) | KR101260597B1 (en) |
| CN (1) | CN101346806B (en) |
| TW (1) | TWI343945B (en) |
| WO (1) | WO2007077886A1 (en) |
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| JP2008280229A (en) * | 2007-04-13 | 2008-11-20 | Hitachi Chem Co Ltd | Manufacturing process of surface-modified silicon dioxide particles and polishing liquid |
| JP5327050B2 (en) * | 2007-07-30 | 2013-10-30 | 日立化成株式会社 | Polishing liquid for metal and polishing method |
| US20090056231A1 (en) * | 2007-08-28 | 2009-03-05 | Daniela White | Copper CMP composition containing ionic polyelectrolyte and method |
| WO2009128430A1 (en) | 2008-04-15 | 2009-10-22 | 日立化成工業株式会社 | Polishing solution for metal films and polishing method using the same |
| JP5826986B2 (en) * | 2008-05-01 | 2015-12-02 | Jsr株式会社 | Chemical mechanical polishing aqueous dispersion and chemical mechanical polishing method |
| KR101279968B1 (en) * | 2008-12-31 | 2013-07-17 | 제일모직주식회사 | Cmp slurry composition |
| KR20150014924A (en) * | 2012-04-18 | 2015-02-09 | 가부시키가이샤 후지미인코퍼레이티드 | Polishing composition |
| US10406652B2 (en) * | 2014-03-28 | 2019-09-10 | Fujimi Incorporated | Polishing composition and polishing method using the same |
| JP2016035040A (en) * | 2014-08-01 | 2016-03-17 | 株式会社フジミインコーポレーテッド | Polishing composition |
| JP2016056292A (en) * | 2014-09-10 | 2016-04-21 | 株式会社フジミインコーポレーテッド | Polishing composition and production process therefor, polishing method, and substrate and production process therefor |
| KR101682085B1 (en) * | 2015-07-09 | 2016-12-02 | 주식회사 케이씨텍 | Slurry composition for tungsten polishing |
| KR101715050B1 (en) * | 2015-11-05 | 2017-03-13 | 주식회사 케이씨텍 | Slurry composition for tungsten polishing |
| US11326049B2 (en) * | 2016-09-21 | 2022-05-10 | Fujimi Incorporated | Composition for surface treatment |
| US11319460B2 (en) | 2017-03-23 | 2022-05-03 | Fujimi Incorporated | Polishing composition |
| KR102611598B1 (en) * | 2017-04-27 | 2023-12-08 | 주식회사 동진쎄미켐 | Aqueous slurry composition for chemical mechanical polishing |
| US11401441B2 (en) | 2017-08-17 | 2022-08-02 | Versum Materials Us, Llc | Chemical mechanical planarization (CMP) composition and methods therefore for copper and through silica via (TSV) applications |
| US10465096B2 (en) | 2017-08-24 | 2019-11-05 | Versum Materials Us, Llc | Metal chemical mechanical planarization (CMP) composition and methods therefore |
| CN108527012A (en) * | 2018-05-21 | 2018-09-14 | 浙江工业大学 | A kind of device carrying out big plane polishing using liquid metal polishing fluid |
| SG10201904669TA (en) * | 2018-06-28 | 2020-01-30 | Kctech Co Ltd | Polishing Slurry Composition |
| KR20200032601A (en) * | 2018-09-18 | 2020-03-26 | 주식회사 케이씨텍 | Polishing slurry composition |
| US20200277514A1 (en) | 2019-02-28 | 2020-09-03 | Versum Materials Us, Llc | Chemical Mechanical Polishing For Copper And Through Silicon Via Applications |
| CN110238746B (en) * | 2019-06-28 | 2021-04-20 | 大连理工大学 | Chemical mechanical polishing method and polishing solution for FV520B material impeller blade |
| CN110434680A (en) * | 2019-07-19 | 2019-11-12 | 大连理工大学 | A kind of chemical mechanical polishing liquid and polishing method of propeller |
| CN114213978B (en) * | 2021-12-23 | 2022-08-02 | 广东欣科兴五金制品有限公司 | Copper alloy surface polishing solution and preparation method thereof |
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| JP2004311565A (en) | 2003-04-03 | 2004-11-04 | Hitachi Chem Co Ltd | Metal polishing solution and polishing method |
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| JP2001127019A (en) * | 1999-10-29 | 2001-05-11 | Hitachi Chem Co Ltd | Polishing fluid for metal and method for polishing substrate using the same |
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2006
- 2006-12-27 KR KR1020117006918A patent/KR101260597B1/en not_active IP Right Cessation
- 2006-12-27 US US12/159,419 patent/US8791019B2/en active Active
- 2006-12-27 WO PCT/JP2006/326106 patent/WO2007077886A1/en active Application Filing
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- 2006-12-27 TW TW095149210A patent/TWI343945B/en active
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| WO2003094216A1 (en) | 2002-04-30 | 2003-11-13 | Hitachi Chemical Co., Ltd. | Polishing fluid and polishing method |
| JP2004311565A (en) | 2003-04-03 | 2004-11-04 | Hitachi Chem Co Ltd | Metal polishing solution and polishing method |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2007077886A1 (en) | 2007-07-12 |
| JP4952584B2 (en) | 2012-06-13 |
| CN101346806A (en) | 2009-01-14 |
| KR20080070074A (en) | 2008-07-29 |
| TW200730614A (en) | 2007-08-16 |
| KR20110048563A (en) | 2011-05-11 |
| JP2012119697A (en) | 2012-06-21 |
| US20100178765A1 (en) | 2010-07-15 |
| US8791019B2 (en) | 2014-07-29 |
| TWI343945B (en) | 2011-06-21 |
| CN101346806B (en) | 2010-09-29 |
| JPWO2007077886A1 (en) | 2009-06-11 |
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